Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

• the present invention relates to 2- (pyridin-2-yl) -pyrimidines and their use for controlling harmful fungi and crop protection products containing such compounds as an active ingredient.
• the EP-A 234 104 describes 2- (pyridin-2-yl) -pyrimidines which have an alkyl group in the 6-position of the pyridine radical and which may have a fused saturated 5- or 6-membered ring in the 3,4-position of the pyrimidine ring.
• the compounds are suitable for controlling phytopathogenic fungi (harmful fungi).
• the EP-A 259 139 describes 2- (pyridin-2-yl) -pyrimidines of the general formula A. wherein a is 0, 1, 2, 3, 4 or 5, R a is halogen, lower alkyl, lower alkoxy or haloalkyl, R b and R c are independently hydrogen or C 1 -C 4 alkyl, R d is hydrogen or Lower alkyl means R e is hydrogen, lower alkyl or halogen or together with R d is propane-1,3-diyl or butane-1,4-diyl and R f is, inter alia, hydrogen, alkyl, lower alkoxy or lower alkylthio.
• the present invention is therefore based on the object to provide new compounds with better fungicidal activity and / or better crop compatibility.
• the present invention thus provides the 2- (pyridin-2-yl) -pyrimidines of the general formula I and their agriculturally acceptable salts.
• the present invention further provides an agent for controlling harmful fungi, comprising at least one 2- (pyridin-2-yl) pyrimidine compound of the general formula I and / or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
• the compounds of the formula I and their tautomers can have one or more centers of chirality and are then present as pure enantiomers or pure diastereomers or as mixtures of enantiomers or diastereomers.
• the invention relates to both the pure enantiomers or diastereomers and mixtures thereof.
• Agriculturally useful salts are, above all, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the fungicidal activity of the compounds I.
• the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion the desired one to four C 1 - C 4 -alkyl substituents and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, further phosphonium ions, sulfonium ions, preferably tri (C 1 -C 4 -alkyl) sulfonium and sulfoxonium ions, preferably tri (
• Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 alkanoic acids, preferably formate , Acetate, propionate and butyrate. They may be formed by reaction of I with an acid of the corresponding anion, preferably hydrochloric, hydrobromic, sulfuric, phosphoric or nitric acid.
• a first embodiment of the invention relates to compounds in which n is 3, 4 or 5 and in particular 3 or 4, R 2 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 - Alkoxy, C 1 -C 4 haloalkoxy, hydroxy, halogen, CN or NO 2 and the other variables have the meanings given above, in particular have the meanings mentioned below as preferred.
• a second embodiment of the invention relates to compounds in which n is 1 or 2 and especially 2, R 2 is C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, hydroxy, halogen, CN or NO 2 and the other variables have the meanings mentioned above, in particular have the meanings mentioned below as preferred.
• radicals R 11 , R 12 , R 13 , R 14 or R 15 are different from hydrogen, then advantageously only one of the radicals other than hydrogen is different from halogen or methyl. Especially when one of the radicals R 11 , R 12 , R 13 , R 14 or R 15 is different from hydrogen, halogen or methyl, then the remaining radicals R 11 , R 12 , R 13 , R 14 , R 15 are selected from halogen and hydrogen.
• radicals P are in particular those in which R 11 , R 12 , R 13 , R 14 and R 15 together have the meanings given in a row of Table A: Table A: R 11 R 12 R 13 R 14 R 15 1 H H H H H 2 F H H H 3 H F H H H 4 H H F H H 5 Cl H H H H 6 H Cl H H H H 7 H H Cl H H 8th br H H H H 9 H br H H H 10 H H br H 11 F F H H H H 12 F H F H H H 13 F H H H H F 14 H F F H H 15 H F H F H F H 16 Cl Cl H H H 17 Cl H Cl H H 18 Cl H H Cl H 19 H Cl Cl H H 20 H Cl H Cl H 21 F Cl H H H 22 Cl F H H H 23 F H Cl H H 24 F H H Cl H 25 F H H Cl 26 Cl H F H H 27 H Cl F H H 28 H F Cl H H 29 H Cl H F H 30 F H F H F 31 F F F F F F F F F F F F F F F F
• a particularly preferred embodiment of the invention are the compounds of general formula Ia, wherein R 11 , R 12 , R 13 , R 14 and R 15 have the meanings given above and in particular have the meanings given as preferred and R 2 has the abovementioned meanings different from H and C 1 -C 4 -alkyl and in particular for C 1 -C 4 alkoxy, especially methoxy, ethoxy, isopropyloxy, tert-butyloxy, C 1 -C 2 fluoroalkyloxy, especially difluoromethoxy or trifluoromethoxy, CN, NO 2 or OH.
• Examples of these are the compounds of the formula Ia given in the following Tables 1 to 9 in which R 11 , R 12 , R 13 , R 14 and R 15 together have the meaning given in one of lines 2 to 144 of Table A.
• R 11 , R 12 , R 13 , R 14 and R 15 have the meanings given above and in particular have the meanings given as preferred and R 2 has the meanings given above and in particular C 1 -C 4 alkyl, especially methyl, ethyl , n-propyl, isopropyl, n-butyl, 2-butyl or tert-butyl, C 1 -C 4 -alkoxy, especially methoxy, ethoxy, isopropyloxy or tert-butyloxy, C 1 -C 2 -fluoroalkyl, especially trifluoromethyl or pentafluoroethyl, C 1 -C 2 fluoroalkyloxy, especially difluoromethoxy or trifluoromethoxy, halogen, especially fluorine, chlorine or bromine, CN, NO 2 or OH. Examples of these are the compounds of the formula Ib indicated in the following Table
• a further, particularly preferred embodiment of the invention are the compounds of general formula Ic wherein R 11 , R 12 , R 13 , R 14 and R 15 have the meanings given above and in particular have the meanings given as preferred and R 2 has the abovementioned meanings different from H and C 1 -C 4 -alkyl and in particular for C 1 -C 4 alkoxy, especially methoxy, ethoxy, isopropyloxy, tert-butyloxy, C 1 -C 2 fluoroalkyloxy, especially difluoromethoxy or trifluoromethoxy, CN, NO 2 or OH.
• Examples of these are the compounds of the formula Ic given in the following Tables 31 to 39, in which R 11 , R 12 , R 13 , R 14 and R 15 together have the meaning given in one of lines 2 to 144 of Table A.
• R 11 , R 12 , R 13 , R 14 and R 15 have the meanings given above and in particular have the meanings given as being preferred, and R 2 are those indicated above
• C 1 -C 4 -alkyl especially methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or tert-butyl, C 1 -C 4 -alkoxy, especially methoxy, Ethoxy, isopropyloxy or tert-butyloxy, C 1 -C 2 fluoroalkyl, especially trifluoromethyl or pentafluoroethyl, C 1 -C 2 fluoroalkyloxy, especially difluoromethoxy or trifluoromethoxy, halogen, especially fluorine, chlorine or bromine, CN, NO 2 or OH stands. Examples of these are the compounds of the formula Id given in the following Tables
• a further preferred embodiment of the invention are the compounds of general formula Ie, wherein R 11, R 12, R 13, R 14 and R 15 have the meanings given above and in particular the meanings given as being preferred and R 2 has the meanings indicated above, and in particular C 1 -C 4 alkyl, especially methyl, ethyl , n-propyl, isopropyl, n-butyl, 2-butyl or tert-butyl, C 1 -C 4 -alkoxy, especially methoxy, ethoxy, isopropyloxy or tert-butyloxy, C 1 -C 2 -fluoroalkyl, especially trifluoromethyl or pentafluoroethyl, C 1 -C 2 fluoroalkyloxy, especially difluoromethoxy or trifluoromethoxy, halogen, especially fluorine, chlorine or bromine, CN, NO 2 or OH. Examples of these are the compounds of the formula Ie given in the following Tables 61
• R 1 , R 3 , m, n and k have the meanings given above.
• R 2a is H, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, NO 2 or OH.
• R is H or C 1 -C 4 -alkyl or forms with other molecules IIa a phenylboronic anhydride.
• R ' is C 1 -C 4 alkyl and especially methyl.
• a 2-bromopyridine is reacted with a phenylboronic acid derivative of the general formula IIa under the conditions of a Suzuki coupling, ie in the presence of a platinum metal catalyst and in particular in the presence of a palladium catalyst under known reaction conditions, as for example Acc. Chem. Res. 15, p. 178-184 (1982 ) Chem. Rev. 95, pp. 2457-2483 (1995 ), and the literature cited therein, as well as from J. Org. Chem. 68, p. 9412 (2003 ) are known.
• catalysts are tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride, bis (acetonitrile) palladium (II) chloride, [1,1'-bis (diphenylphosphino) ferrocene] - palladium (II) chloride-dichloromethane complex, bis [1,2-bis (diphenylphosphine) ethane] palladium (0) and [1,4-bis (diphenylphosphine) butane] palladium (II) chloride.
• the amount of catalyst is usually 0.1 to 10 mol%.
• the resulting 2-phenylpyridine of the formula III in step ii) is converted by treatment with a peracid according to methods known per se into the 2-phenylpyridine-N-oxide of the formula IV.
• the conversion of III into IV can be carried out analogously to known processes, for example by treatment of III with hydrogen peroxide in an organic acid such as formic acid, acetic acid, chloroacetic acid or trifluoroacetic acid (see, for example, US Pat. J. Org. Chem. 55, pp. 738-741 (1990 ) and Organic Synthesis, Collect. Vol. IV, pp.
• step iii) The conversion of the 2-phenylpyridine-N-oxide of the formula IV into the nitrile V in step iii) can be carried out, for example, by a modified Reissert-Henze reaction analogous to that described in J. Org. Chem. 48, p. 1375 (1983 ) and J. Org. Chem. 55, pp. 738-741 (1990 ) methods described by reaction of IV with a trialkylsilyl cyanide such as trimethylsilyl cyanide in the presence of chloroformic acid-N, N-dimethylamide.
• a trialkylsilyl cyanide such as trimethylsilyl cyanide
• the nitrile V may be prepared from the 2-phenylpyridine N-oxide IV by successive reaction with dimethyl sulfate followed by cyanide ions, e.g. B. with sodium or potassium cyanide in analogy to in Tetrahedron p. 4947 (1985 ) are produced.
• cyanide ions e.g. B. with sodium or potassium cyanide in analogy to in Tetrahedron p. 4947 (1985 ) are produced.
• step iii) 2-cyano-6-phenylpyridine compound of general formula V is then in step iv) after the in US 4,873,248 method converted into the amidinium hydrochloride of the formula VI.
• the conversion is carried out by successive treatment with alkali metal alcoholate, such as sodium methoxide or ethanolate and subsequent reaction with ammonium chloride.
• alkali metal alcoholate such as sodium methoxide or ethanolate
• ammonium chloride instead of the hydrochlorides, the hydrobromides, acetates, sulfates or formates can also be used in the subsequent step v).
• the amidinium hydrochloride of the formula VI thus obtained in step v) is reacted with a dialkylaminomethylenecycloalkanone of the formula VII (enaminoketone VII) in the presence of a base, preferably an alkali metal alcoholate, such as sodium methylate or sodium ethylate.
• a base preferably an alkali metal alcoholate, such as sodium methylate or sodium ethylate.
• a base preferably an alkali metal alcoholate, such as sodium methylate or sodium ethylate.
• ⁇ -oxoacetals of the formula VIIa can also be used in step v)
• R is C 1 -C 4 -alkyl and in particular methyl or ethyl
• the reaction VI with VIIa can be carried out in analogy to that described in EP-A 259139 described method (a), which are incorporated herein by reference.
• Dialkylaminomethylenecycloalkanones of the formula VII are known or can be prepared on the basis of known methods [see, for example, US Pat. B. WO 2001/087845 . Tetrahedron 50 (7), pp. 2255-2264 (1994 ); Synthetic Communications 28 (10), 1743-1753 (1998 ) or Tetrahedron Letters 27 (23), 2567-70 (1986 )].
• ⁇ -Oxoacetale of formula VIIa are also known, for. B. off EP 259139 , or can be purchased commercially.
• R, R ', R 1 , R 3 , m, n and k have the meanings given above.
• R 2a is H, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl. Hal stands for bromine or chlorine.
• R, R 1 and m have the meanings given above.
• R 2a is C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy or NO 2 .
• Hal and Hal * independently of one another are chlorine or bromine, where Hal * can also be iodine.
• the conversion of the 2-halopyridine X into the 2-cyanopyridine XI in step ix) succeeds according to standard methods of organic chemistry by reacting X with cyanide ions, eg. With sodium or potassium cyanide (see EP-A 97460 , Preparation Example 1), copper (I) cyanide (see EP-A 34917 , Preparation Example 3) or trimethylsilyl cyanide. Subsequently, the compound XI thus obtained is converted into the pyridine N-oxide XII in analogy to the methods explained in Scheme 1, step ii) (step x).
• step xi) the reaction of XII with a halogenating agent such as POCl 3 or POBr 3 , to obtain the corresponding compound VII.
• a halogenating agent such as POCl 3 or POBr 3
• the halogenating agent is generally used in excess, based on the stoichiometry of the reaction.
• the reaction can be carried out in an inert organic solvent and is often carried out in the absence of a solvent, in which case the halogenating agent usually acts as a solvent.
• the reaction temperature is usually in the range of 20 ° C to the boiling point of the halogenating agent.
• the compound VII can be converted into the compound I according to the method shown in Scheme 2.
• phenylgrignard compounds of the general formula IIb can also be used in Scheme 1 step, i), Scheme 2 step viii) and Scheme 3, step xii).
• step xii) is then carried out in the presence of the aforementioned palladium catalysts or in the presence of tris (acetylacetonato) iron (III) (see Tetrahedron Lett. P. 3547 (2002 )) under optionally slightly modified conditions, wherein the catalyst is usually used in an amount of 0.2 to 8 mol%, in particular 0.5 to 5 mol%, based on the Grignard compound IIb to be coupled.
• Particularly preferred catalyst is [1,4-bis (diphenylphosphine) -butane] palladium (II) chloride.
• the reactions are generally carried out at temperatures in the range of -40 to +120 ° C and in particular in the range of 20 to 100 ° C.
• the reactions are usually carried out in an inert, aprotic organic solvent, preferably an ether and in particular a cyclic ether such as tetrahydrofuran or in a mixture of various aprotic inert solvents, preferably one of the solvents is a cyclic ether such as tetrahydrofuran.
• tetrahydrofuran / N-methylpyrrolidone examples include tetrahydrofuran / toluene or xylene, tetrahydrofuran / dioxane, tetrahydrofuran / N, N-dimethylpropyleneurea (DMPU) and tetrahydrofuran / sulfolane.
• DMPU N-dimethylpropyleneurea
• n, R 3 and k have the meanings mentioned above.
• R 2b is H, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy and in particular CN.
• Hal * is chlorine, bromine or especially iodine.
• the preparation of the Grignard compound XIV from the 2-halopyridine XIII can be carried out according to methods known per se, as described for example in Synlett p. 1359 (1998 ) are described.
• the subsequent coupling of XIV with the 2-chloropyrimidine compound XV in step xiv) is carried out analogously to the already described coupling of Grignard compounds IIb.
• the coupling is carried out in the presence of a transition metal catalyst of a metal of group 8 to 10 (according to IUPAC 1989), in particular a palladium, nickel or iron catalyst.
• a transition metal catalyst of a metal of group 8 to 10 accordinging to IUPAC 1989
• a palladium, nickel or iron catalyst in particular a palladium, nickel or iron catalyst.
• the reaction is carried out in a conventional solvent, for example an ether such as diethyl ether, dioxane, tetrahydrofuran, an aromatic hydrocarbon such as toluene or xylenes, or an aprotic amide, lactam or urea such as N-methylpyrrolidone or dimethylpropyleneurea or in mixtures of these solvents, in particular mixtures containing at least one ether.
• the reaction temperatures are generally in the range of -40 to +120 ° C and in particular in the range of 20 to 100 ° C. Because of further details will be on the in J. Am. Chem. Soc. 124, p. 13856 (2002 ) Chem. Pharm. Bull., P. 4533 (1983 ) and Chem. Pharm. Bull., S. 2005 (1984 ), which can be applied in an analogous manner to the coupling of XIV with XV.
• step xv The compound XVI thus obtained is then converted into the N-oxide XVII in step xv).
• step xv the procedure to step ii) in Scheme 1 or step x) in Scheme 3 Said reference.
• step xvi) the N-oxide XVII is reacted in analogy to step xi in Scheme 3 with a halogenating agent such as POCl 3 or POBr 3 to give the 2-halogeno compound IX of Scheme 2.
• a halogenating agent such as POCl 3 or POBr 3
• This is then reacted according to the method given in Scheme 2 step viii) with a phenylboronic acid compound IIa or the corresponding Grignard compound IIb, to obtain the compound of general formula I.
• reaction mixtures obtained by the methods shown in Schemes 1 to 4 are worked up in a conventional manner, for. B. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products.
• the intermediate and end products fall z. T. in the form of colorless or pale brownish, viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature of volatile fractions. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or digestion.
• the compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Basidiomycetes. They are in part systemically effective and can be used in crop protection as foliar and soil fungicides.
• the compounds I are also suitable for controlling harmful fungi such as Paecilomyces variotii in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
• harmful fungi such as Paecilomyces variotii in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
• the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients.
• the application can be done both before and after the infection of the materials, plants or seeds by the fungi.
• the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% of active ingredient.
• the application rates in the application in crop protection depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.
• the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.
• the compounds I can be converted into the customary formulations, for. As solutions, emulsions, suspensions, dusts, powders, pastes and granules.
• the application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.
• surface-active substances are alkali metal, alkaline earth metal, ammonium salts of ligninsulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, Alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethyleneoctylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, Tristearylphen
• emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg.
• mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg.
• Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
• Granules, for. B. coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers.
• Solid carriers are z.
• mineral earths such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such.
• Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
• the formulations generally contain between 0.01 and 95 wt .-%, preferably between 0.1 and 90 wt .-% of the active ingredient.
• the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
• the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, for. B. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring are applied.
• the forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.
• Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
• the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. But it can also be effective substance wetting, adhesion, dispersing or emulsifying agents and possibly Solvent or oil concentrates are prepared, which are suitable for dilution with water.
• the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
• the active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
• UUV ultra-low-volume
• wetting agents To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents can be added to the inventive compositions in a weight ratio of 1:10 to 10: 1.
• compositions of the invention may also be present in the application form as fungicides together with other active ingredients, the z.
• fungicides As with herbicides, insecticides, growth regulators, fungicides or with fertilizers.
• fertilizers When mixing the compounds I or the agents containing them in the application form as fungicides with other fungicides is obtained in many cases, an enlargement of the fungicidal spectrum of activity.
• the title compound can be prepared in analogy to the steps 1.4 and 1.5 of Example 1, using instead of 2-Dimethylaminomethylencycloheptanon the corresponding hexanone.
• the title compound can be prepared in analogy to the steps 1.4 and 1.5 of Example 1, using instead of 2-Dimethylaminomethylencycloheptanon the corresponding hexanone.
• Example 1.4 6-chloro-5-methyl-pyridine-2-carbonitrile was converted into the 6-bromo-5-methylpyridine-2-carboxamidine hydrochloride. Subsequently, this was prepared analogously to Example 2.2 2- (6-chloro-5-methyl-pyridin-2-yl) -5,6,7,8-tetrahydroquinazoline.
• the compound was prepared starting from 2-cyano-5-methylpyridine under the conditions given for example 1.4.
• the compound was prepared starting from 2-methylpyridine-2-carboxamidine hydrochloride under the conditions given for example 2.2.
• the active compounds were prepared separately as a stock solution with 0.25 wt .-% active ingredient in acetone or DMSO. To this solution was added 1% by weight of Wettol® EM 31 emulsifier (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and diluted with water according to the desired concentration.
• Wettol® EM 31 emulsifier wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
• the active compounds were prepared as a stock solution with 25 mg of active ingredient which was mixed with a mixture of acetone and / or DMSO and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume Ratio solvent emulsifier of 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.
• Uniperol® EL wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
• Paprika leaves of the cultivar "Neusiedler Ideal Elite" were, after 2 to 3 leaves had developed well, sprayed to drip point with an aqueous suspension in the drug concentration below.
• the treated plants were inoculated with an aqueous spore suspension of Botrytis cinerea in a 2% aqueous biomalt solution having a density of 1.7 x 10 6 spores / ml.
• the plants were placed in a climatic chamber at temperatures between 22 and 24 ° C and high humidity. After 5 days, the extent of fungal attack was determined visually by the infestation of the leaf area.
• Leaves of pot fry were sprayed to drip point with aqueous suspension in the concentration of active compound given below.
• the undersurfaces of the leaves were inoculated with an aqueous sporangia suspension of Plasmopara viticola .
• the vines were first placed for 48 h in a saturated with water vapor chamber and then in the greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed for 16 hours in the chamber saturated with water vapor to accelerate the outbreak of sporangia. Then the extent of the infestation development on the undersides of the leaves was determined.
• Leaves of potted tomato plants of the cultivar "Golden Queen" were sprayed to drip point with an aqueous suspension in the concentration of active compound specified below. The next day, the leaves were infected with an aqueous spore suspension of Alternaria solani in a 2% biomalt solution with a density of 0.17 x 10 6 spores / ml. Subsequently, the plants were placed in a saturated with water vapor chamber at temperatures of 20 to 22 ° C. After 5 days, the disease on the untreated, but infected plants had developed so strongly that the infestation could be determined visually.
• Leaves of potted barley seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. 24 hours after the spray coating had dried, the plants were treated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch, inoculated. Subsequently, the test plants were placed in the greenhouse at temperatures between 20 and 24 ° C and 95 to 100% relative humidity. After 6 days, the extent of the disease development was determined visually by the involvement of the leaf area in%.
• Paprika leaves of the cultivar "Neusiedler Ideal Elite" were, after 2 to 3 leaves had developed well, sprayed to drip point with an aqueous suspension in the drug concentration below.
• the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 10 6 spores / ml in a 2% aqueous biomalt solution.
• the test plants were placed in a climatic chamber at temperatures between 22 and 24 ° C, darkness and high humidity. After 5 days, the extent of fungal attack was determined visually in% from the infestation of the leaf area.
• Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. The following day, the leaves were infected with an aqueous sporangium suspension of Phytophthora infestans . Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 18 and 20 ° C. After 6 days, the late blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.

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  • 2005-07-22 TW TW094125014A patent/TW200610760A/zh unknown
  • 2005-07-22 CA CA002573366A patent/CA2573366A1/fr not_active Abandoned
  • 2005-07-22 WO PCT/EP2005/008039 patent/WO2006010570A1/fr active Application Filing
  • 2005-07-22 DE DE502005009098T patent/DE502005009098D1/de active Active
  • 2005-07-22 PL PL05761662T patent/PL1773806T3/pl unknown
  • 2005-07-22 NZ NZ552589A patent/NZ552589A/en unknown
  • 2005-07-22 AT AT05761662T patent/ATE458728T1/de active
  • 2005-07-22 PT PT05761662T patent/PT1773806E/pt unknown
  • 2005-07-22 DK DK05761662.5T patent/DK1773806T3/da active
  • 2005-07-22 ES ES05761662T patent/ES2340299T3/es active Active
  • 2005-07-22 EP EP09179926A patent/EP2172465A1/fr not_active Withdrawn
  • 2005-07-22 EP EP09179928A patent/EP2172466A1/fr not_active Withdrawn
  • 2005-07-22 AR ARP050103056A patent/AR050265A1/es unknown
  • 2005-07-22 MX MX2007000620A patent/MX2007000620A/es active IP Right Grant
  • 2005-07-22 US US11/632,342 patent/US7786043B2/en not_active Expired - Fee Related
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• 2006
  • 2006-12-28 IL IL180441A patent/IL180441A0/en unknown
• 2007
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  • 2007-01-17 MA MA29615A patent/MA28737B1/fr unknown
  • 2007-02-21 ZA ZA200701518A patent/ZA200701518B/xx unknown
• 2010
  • 2010-04-29 HR HR20100246T patent/HRP20100246T1/hr unknown
  • 2010-05-20 CY CY20101100441T patent/CY1110343T1/el unknown
  • 2010-07-21 US US12/840,392 patent/US20100286175A1/en not_active Abandoned
• 2011
  • 2011-02-09 AU AU2011200524A patent/AU2011200524A1/en not_active Abandoned

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